Chemosphere 46 (2002) 109±113

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Ozonation of hydrolyzed azo dye reactive yellow 84 (CI)
M. Koch a, A. Yediler

b,*

, D. Lienert a, G. Insel c, A. Kettrup

c

a

c

Chair of Ecological Chemistry, Technical University of Munich, 85350 Freising-Weihenstephan, Germany
b
Institute of Ecological Chemistry, GSF±National Research Center of Environment and Health,
Ingolstadter Landstr. 1, 85764 Neuherberg, Germany
Environmental Engineering Department, Civil Engineering Faculty, Istanbul Technical University, 80626 Maslak, Istanbul, Turkey
Received 20 September 2000; received in revised form 27 February 2001; accepted 22 March 2001

Abstract
The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the eciency of such a system is a better understanding of the mechanisms involved
during the degradation processes. Ozonation has been applied to many ®elds in water and wastewater treatment.
Especially for textile mill e‚uents ozonation can achieve high color removal, enhance biodegradability, destroy phenols
and reduce the chemical oxygen demand (COD). However, little is known about the reaction intermediates and
products formed during ozonation. This work deals with the degradation of hydrolyzed Reactive Yellow 84 (Color
Index), a widely used azo dye in textile ®nishing processes with two monochlorotriazine anchor groups. Ozonation of
the hydrolyzed dye in ultra pure water was performed in a laboratory scale cylindric batch reactor. Decolorization,
determined by measuring the light absorbance at the maximum wavelength in the visible range (400 nm), was almost
complete after 60 and 90 min with an ozone concentration of 18.5 and 9.1 mg/l, respectively. The TOC/TOC0 ratio after
ozonation was about 30%, the COD was diminished to 50% of the initial value. The BOD5 =COD ratio increased from
0.01 to about 0.8. Oxidation and cleavage of the azo group yield nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused increases in the amount of sulfate. Formic acid and oxalic acid were identi®ed as main oxidation
products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at de®ned time intervals during ozonation. Ó 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Ozone; Reactive Yellow 84; Dyeing wastewater; Textile industry

1. Introduction
Wastewater from textile industry is generally characterized by high chemical levels and biochemical oxygen demand, total suspended solids and strong color.
Neither simple chemical nor biological treatment has
proved adequate in decolorization and sucient depletion in organic matter so far. Numerous publications
refer to biological (either aerobic or anaerobic) and/or

*

Corresponding author. Tel.: +49-(0)89-3187; fax: +49(0)89-3187-3371.
E-mail address: yediler@gsf.de (A. Yediler).

physico-chemical treatment of dyeing wastewater. The
application of these methodologies is restricted in scale
of operation since their eciencies highly depend on the
pollution pro®le of the wastewater (Lin and Lin, 1993;
Schr
oder, 1994; Shu et al., 1994; Ince et al., 1997; Krull
et al., 1998).
Surplus dyes which are not ®xed to the fabric
throughout the dyeing process ± e.g. hydrolyzed reactive
azo dyes ± are the main organic components in e‚uents
from textile mills. They are complex organic compounds
containing various substituted aromatic nuclei. Their
low BOD5 =COD ratio values (usually less than 0.1) indicate their resistance to conventional biological treatment. Additional oxidative treatment steps ± e.g.

0045-6535/02/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
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The ozone consumption was calculated by means of the monitored ozone concentration at the reactor outlet (Fig.. 1998). Lopez et al. little is known about the reaction intermediates and products formed during ozonation. The ozone concentration was determined by an ozone measuring device model Ozon Meûger at (Erwin Sander Elektroapparatebau). 2). Ueltzen). Main characteristics of RY 84 are represented in Fig. 400 nm] COD BOD5 =COD pH TOC Conductivity 295 m 1 160 mg/l 0. 3 the calculated ozone uptake is compared to the overall used ozone amount. Integration of the ozone concentration as a function of time resulted in ozone uptake by the aqueous solution during ozonation.3 45 mg/l 180 lS=cm Ozone was generated from dried air by an ozone generator (Ozon Erzeuger 24 g of Erwin Sander Elektroapparatebau. containing RY 84 in 80% purity. HPIC-analysis of organic and inorganic anions was performed by a Dionex model 4000 ion chromatograph (Dionex. The obvious lower ascending slope of the ozone uptake curve indicates the low reactor e€ectiveness as a process engineering problem. 1996. Hydrolysis of RY 84 was accomplished by dissolving the dye formulation in water (c ˆ 200 mg/l).5 ml/min. USA) equipped with an IonPac HPICE-AS11 column (Dionex) and operating in suppressed conductivity detection mode.110 M. BOD5 was determined before and after ozonation treatment by the standard method DIN EN 1899-2. 1. injected with a volume of 50 ll by an automatic sampler.01 6. Tzitzi et al. conductivity and inorganic/ organic anions by high performance ion chromatography (HPIC). pH. total organic carbon (TOC). 1992. a widely used dye in textile ®nishing processes with two monochlorotriazine anchor groups. Experimental The reactive azo dye Reactive Yellow 84 (RY 84. . D uren. To determine the ozone consumption during the ozonation of RY 84 (c ˆ 200 mg/l) a further experiment was run without sampling.. Koch et al. TOC was measured on a Schimadzu model 2000 TOC analyzer. COD determination was conducted with commercially available test kits of Macherey & Nagel. Koyuncu and Afsar. Color Index) was obtained from BASF as a commercially available dye formulation designated as Procion Yellow H-E4R. Ozonation has been applied to many ®elds in water and wastewater treatment (Schulz et al. Germany. were eluted by a NaOH/water gradient at a ¯ow rate of 1. CA. / Chemosphere 46 (2002) 109±113 ozonation ± are promising techniques to reduce these recalcitrant wastewater loads. High color removal eciency. For this purpose UV/visible absorption spectra were recorded using a Cary 1 spectrophotometer (Varian). This work focuses on the ozonation of the hydrolyzed reactive azo dye Reactive Yellow 84 (Color Index). adjusting with 2 N NaOH to pH 10 and boiling for 3 h (95°C) under re¯ux conditions. Samples (20 ml) were withdrawn at de®ned time intervals and analyzed for UV/vis absorbance. However. 1994). Samples. Decolorization capacity of ozonation process was determined by absorbance measurements at the maximum visible absorbance wavelength (400 nm). destruction of phenolic compounds as well as considerable reduction in chemical oxygen demand (COD) can be attained by ozonation for textile mill e‚uents (Gahr et al. Ozonation was performed in a cylindric glass reactor (volume 1. 1994.2 l) by bubbling the ozone/air mixture at a volume stream of 20 l/h through a sintered glass ®lter (pore size 50±80 lm) into the hydrolyzed dyestu€ solution. Characteristics (initial values) of hydrolyzed RY 84 water solution prior to ozonation are as follows: Absorbance [translucent color value (TCV). 1.. Sunnyvale.. enhanced biodegradability. In Fig. Reactor e€ectiveness may be enhanced by many Fig. Characteristics of Reactive Yellow 84 (CI). 2. COD.

6). The TOC=TOC0 ratio . 4. respectively (Fig. respectively. pH and conductivity during the ozonation of hydrolyzed RY 84 (c ˆ 200 mg/l. 3. Fig. 6. min with O3 concentration of 9.1 to about 3. 5. process options. Ozone feeding rate: 6. e. RY 84 concentration: 200 mg/l. Koch et al.1 mg/l.M. Due to the production of organic and inorganic acid anions the pH decreased during ozonation from 6.7 mg/min. The corresponding TOC removal rates were 30% and 25% under identical operational conditions. / Chemosphere 46 (2002) 109±113 111 Fig. 3. Results and discussion Decolorization of hydrolyzed RY 84 was almost complete after 60 and 90 min of ozonation with starting ozone concentrations of 18. by modi®cation of the reactor length for longer contact time. RY 84 concentration: 200 mg/l. not being completely mineralized under the prevailing oxidative conditions. COD removal was more ecient than TOC reduction throughout the ozonation process (Fig. Remaining COD and TOC during the ozonation of hydrolyzed RY 84 (c ˆ 200 mg/l) with two di€erent ozone concentrations. These results might be explained by the production of small organic molecular fragments along with the destruction of the dyestu€. Ozone feeding rate: 6.2 whereas the conductivity increased (Fig.5 and 9. Fig. 50% and 40% COD removal rates were obtained after 60 min of ozonation with O3 concentration of 18. by production of smaller bubble sizes or by recycling of the unconsumed ozone. 2. Ozone concentration at the reactor outlet during ozonation of RY 84.1 mg/l. 5). two di€erent ozone concentrations).g. Absorbance (400 nm) during the ozonation of hydrolyzed RY 84 (c ˆ 200 mg/l. 4). two di€erent ozone concentrations).5 mg/l and 90 Fig. Fig. Ozone generation and uptake during ozonation of RY 84.7 mg/min.

1035± 1041. C. Ince.01) of untreated RY 84 solution. Hemmi. Oppermann. To obtain detailed information on the reaction processes during ozonation the resulting oxidation products analysis of organic and inorganic anions were performed. 38. P. nitrate. N.. 1994. D. but the tendencies of the determined parameters during the treatment process are helpful to assess the eciency of ozonation.R. as a partial step of a combined treatment concept ± is a potential technique for decolorization and biodegradability enhancement of wastewater containing hydrolyzed reactive azo dyes. and oxidation and cleavage of the sulfonic acid groups lead to the increasing amount of sulfate during ozonation. Conclusion The results obtained by the experimental study con®rm that ozonation ± i. Tiravanti.e. J. Koyuncu.. Decomposition of dyes in the textile wastewater with ozone. The TOC=TOC0 ratio is helpful to assess the mineralization rate but it has to be taken into account that volatile compounds ± i.H. Health A 31. Hermanutz. 1743±1748. 1996.01 to 0... acetaldehyde ± into the gaseous stream during the ozonation process. Treatment of textile waste e‚uents by ozonation and chemical coagulation. New waste management strategies imply the evaluation of each residue stream individually. 7. 1994. 339±346. 4. Acknowledgements The authors wish to thank The Volkswagen-Foundation for the ®nancial support of this research work (Project-Nr. formate and oxalate and their concentrations during ozonation are shown in Fig.. Ozonation could be competitive in spite of its high energy costs. Otto.1 mg/ l.C... Lin. Fig. H.. ozone concentration ˆ 18. Oxidation and cleavage of the azo and amino groups result in the formation of nitrate.. Bolton. Main oxidation products were identi®ed as sulfate.. Eliminationsverhalten von Schadsto€en gewerblicher Abwasser bei biologischer. J. Adv. Mascolo. 1998.M. 239±245. F. Schr oder. J. F. physikalischer und .H. Due to the decreasing value of pH during ozone treatment it can be assumed that the ozonated solution contains the analyzed organic anions in the form of their corresponding acids. as well as an advantageous method for the removal of organic compounds persistent to biological treatment. The BOD5 =COD ratio increased from 0. Considering the extremely low BOD5 =COD ratio (0.e.C. no unique `best practical treatment option' can be assessed. hydrolyzed RY 84 can be regarded as almost resistant to biological degradation. a case study. Lin. 442±448. 1993. 1997. / Chemosphere 46 (2002) 109±113 is helpful to assess the mineralization rate but the obtained TOC values may not present the total TOC concentrations due to the losses of volatile compounds ± i. It can be thought as an ecient option for advanced treatment of textile e‚uents to satisfy speci®c water reuse criteria. G. 7. 27. Concentrations of sulfate. I. Water Res. Additional investigations are planned to search for further ozonation products i. 30.F. Technol. II/72 146). formate and oxalate during ozonation of hydrolyzed RY 84 …cdye ˆ 200 mg=l. Koch et al. Water Sci. W. 2. Oxid. A. Water Sci. R.M.. formaldehyde. S. nitrate. Biodegradability enhancement of refractory pollutants by ozonation: a laboratory investigation on an azo-dyes intermediate. G. Afsar.81 after 90 min with an ozone concentration of 9. H.. Passino. A. G. It could be applied as a selective measure for the treatment of segregated line streams and is a promising tool for highly ¯exible wastewater treatment concepts. UV/H2 O2 degradation and toxicity reduction of textile azo dyes: Remazol black-B. Ricco..79 after 60 min of ozonation …cO3 ˆ 18:5 mg=l† and to 0. Combined biological and chemical treatment of highly concentrated residual dyehouse liquors. R. sulfonated aromatic compounds. Krull. in order to develop a strategy of separate or combined handling. Technol. 255±263... Since the pollution pro®le of each individual mill varies greatly. Ozonation ± an important technique to comply with new German laws for textile wastewater treatment. Exact mass balance and mineralization rate calculations cannot be made on the basis of the represented results. Technol. References Gahr. Stefan. acetaldehyde ± are withdrawn during ozonation in the gaseous stream and therefore excluded from TOC determination... This indicates an enhanced biodegradability of the dye solution after the ozone treatment. 1998. I.. 38.112 M. formaldehyde..e. Water Sci.5 mg/l). Sch. Di Pinto.e. R.. Technol. Hempel. if partial e‚uents were to be treated. Lopez.

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